Cyclopropyl quaternary ammonium compounds and process of applying to textiles



Patented June 1, 1954 CYCLOPROPYL QUATERNARY AMMONIUM COMPOUNDS AND PROCESS OF APPLY- ING TO TEXTILES vJohn R. Janes, Garden City, N. Y., assignor to Deering Milliken Research Trust, Greenwich, Conn., a nonprofit trust of Maine No Drawing. Application August 31, 1948, Serial No. 47,150

7 Claims. '1

This invention relates to textile finishing compounds, to aprocess of treating textile materials inorder to improve their properties and to the imprevedtextile materials thereby produced.

'Cellulosic, proteinaceous and other textiles have heretofore been rendered water repellent by treating them with water repellent quaternary ammonium compounds containing a long chain aliphatic radical. These compounds are believed to react chemically with the textile, but have only one reactive-functional group. It has now been ascertained that if like compounds are prepared containingitwo unlike functional groups, each of which are. capableof reacting with the textile molecule, additionalmodifications of the physical properties may be obtained. Such modifications include dimensional stability and crease-resistance.

Thus in accordance with this invention, textile materials are treated with quaternary ammonium salts ofcyclopropane derivatives. These compounds'have *a radical containing a cyclopropyhgroupiinkedto the quaternary nitrogen atom and are capable of reacting with the textile'moleculeat both the cyclopropane and the quaternary ammonium groups. The compounds increase. the water repellency of textile materials while: at the. same time softening them and enhancing their dyeing'properties, and usually impart dimensional stabilization or shrinkage controlandcrease resistance to the material as wll,..-possib1y because of the formation of cross linkages between adjacent textile molecules or because of polymerization of the compound or its decomposition products in. situ to form a resin.

COMPGUNDS' OF THE INVENTION R 1! lm-alkyl radical. Typical hydrocarbon radicals are methylene, ethylene, octamethylene, octadecylene decamethylene, benzene, naphthalene, cyclohexane and cyclopentane.

X is an inorganic or organic anion, such as chloride, bromide, iodide, acetate, formate, thiocyanate, nitrate, sulfate, or nitrite.

N (tert) is the residue of a tertiary amine. Typical tertiary amine residues include those in which three nitrogen valences are taken up in one ring, as in pyridine, pyrazine, pyrimidine,

quinoline, isoquinoline, acridine, and phenanthridene, those in which two nitrogen valences are taken up in one ring, as in piperidine, or tetrahydroquinoline or isoquinoline, and a third taken up with an alkyl group, and those in which three valences are taken up with alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl, whether n-, secondary or tertiary.

Within the generic formula set forth above, the compounds of the invention may, as can be seen from the subsequently presented examples, take the form:

Where R is a bivalent radical selected from the group consisting of NH o, c o-, -00 o, -CONH-, o-, -N'HCO 0-,

-NHC ONH-, -o ONHC ONH, OOH2NTIC ONE-- and CH:O 0 ONE- A is a hydrocarbon radical containing from 1 to 20 carbon atoms; m, n, and p are numbers selected from the numbers 0 and 1, subject to the proviso that they cannot all be 0 at the same time and, further, that when m and n are both 1, p is also 1; N(tert) is a tertiary amine; and X is an anion.

When A is trivalent, the formula may assume one of these special forms:

where Z is a bivalent aliphatic, aromatic or cycloaliphatic radical, such as methylene, ethylene, butylene, hexylene, decamethylene, octadeca- 3 methylene, or a benzene, naphthalene, or cyclohexane residue.

These compounds may be prepared in a number of ways.

1. a,'y-Halogen alkanes may be treated with metallic sodium in ether or with zinc in alcohol:

CH: BI'CH: CHzCH-Y l CHY Br The cyclopropionic acid may be used in various conventional syntheses to produce quaternary ammonium salts as shown in the examples. To illustrate, the corresponding amide may be formed, and the latter chloromethylated and +2NaBr ZCzHaOH hydrolyze treated with a. tertiary amine. C3: C13: (CH O) onooon I CHCONH: 2 H01 011, OH:

H, CH:

\ N(tert) /CHCONHCH1N(tert)Cl /CHCONHCHsCl H: on:

Similarly, substituted ureas, carbamates and esters may be prepared.

3. 'y-Halogenated nitriles may be treated with sodium amide in liquid ammonia, and then hydrolyzed to the acid or amide:

GHICI CH! CH: NSNH: (L CHCN Nil-Cl NHa CHgCN 2 lee CH: H: J: CHCOOH CHCONHI Treatment of the nitrile with sodium gives a dimer which may be hydrolyzed to a ketone:

This may be converted to the alcohol and chloromethylated as set forth above.

4. Allyl bromide may be treated with substituted alcohols and chlorine:

C12 CH=CHCE1BI H0 CHzY BICH: CH2

Zn CH-O CH1 CHO CHzY H2O CICH: CH:

where Y is any organic radical, such as one containing halogen, an N(tert)X group, or a group capable of chloromethylation.

These compounds are white or pale-colored viscous oils or solids, soluble or dispersible in Water (benzene, chloroform, ethyl alcohol, carbon tetrachloride, and ethylene dichloride, sparingly soluble in ether and acetone. Most of the compounds are thoroughly stable even in aqueous solution, but some may decompose or polymerize gradually at room temperature after being dissolved in water.

The quaternary ammonium group of the compounds decomposes when heated above C., the reaction being accomplished by liberation of the tertiary amine employed in its formation. The free radical liberated in this reaction, which is of the form:

may react with another free radical to form a dimer, or react with water to form a fatty alco-' hol. If the reaction was brought about in the presence of cellulose, it may react with a hydroxyl group of a cellulose molecule to form an ether of the general structure on; 0elluloseOCHzA-Ci 3 Also, the free radical may decompose further, since the cyclopropane ring may open and react either with the cellulose molecule to form an ether of the general structure or with other cyclopropane residues to form a resin in or about the fibers. This makes possible the formation of cross links between adjacent cellulose molecules of the structure When the compound contains only one cyclopropane and one quaternary ammonium group, linear polymers may be formed by interaction of the decomposition products; if the compound contains three or four functional groups, such as two cyclopropane and/or two quaternary ammonium groups, cross-linked polymers or linear polymers themselves linked to cellulose may be formed.

The particular A linkage may also influence the reaction. If A is an amide, carbamate, or urea residue, for example, polymerisation of the decomposition products is favored.

These postulated reactions are believed responsible for the permanent water repellency, dimensional stability and creaseresistance imparted by these compounds to cellulosic, proteinaceous and other textile materials.

This reaction takes place with cellulosic materials as a class regardless of their physical form, whether fibers, roving, yarns, fabrics or films; typical natural cellulosic materials including cotton, flax, jute, hemp, ramie, linen, sisal, bast and wood pulp. Reaction also occurs with artificial cellulosic films and fibers such as regenerated cellulose, cellulose acetate, cellulose acetate butyrate, cellulose propionate, cellulose acetate propionate and ethyl cellulose. Apparently chemical reactions occur with the protein molecule, probably at the NH group; the compounds react with wool? silk; casein; albumen; alginateand I like proteinaceous-films-orfibers, regardless of theirstage =of'manufacture- They also-give similar results with-fibers formed fromnylon, copolymers =01 yinyl chloride-andvinyl acetate, such as are sold under'the name Vinyon, and copolymers' 'of vinyl chloride and vinylidene chloride, such as aresold under the name Saran.

when thezcompounds ofthe invention are'applied to textile materials and then decomposed, it will'be understood that'anyorall'of the above chemical reactions may occur consecutively-or simultaneously. Thus, the compound may react withthe textile, polymerize insitu the fiber or film to Iowa resin, and alsoreactto form:

a-dimer:

Whenthe-compounds of the invention are applied-to textiles-theproperties of the textile are modified depending upon the particular compound employedand the quantity of thecompound deposited in or-on the material. the material contains between about 0.05 percent and about 20 percent by weight of the compound, its softness and water repellency are increased The softest and most highly water repellent finishes are produced at between about 0.5 "percent and about 10 percent compound by weight of the' material. Best water repellent effects'are obtained with compounds having a cyclopropyl containing radical equivalent in length'to a 10 to 20-carbon straight-chain alkylene group. When the textile material contains between about 2 percent and about 20 percent by weight of certain compounds of the invention, particularly compounds having one or two cyclopropyl-containing organic radicals equivalent in length to an 8 to 16=carbon straight chain alkylene group, its dimensions may be stabilized against either shrinking or stretching. Best stabilization is obtained at betweenabout percent and-about 15 percent compound by weight of the material. Other:textile finishing agents may be-applied to the textile .in order to further modify its properties as is described below.-

THE. PROCESS OF THE INVENTION In brief, the textile material is treated with a solution or dispersion of a compound or mixture ofcompounds of the invention, the solvent wholly orpartially removed by heat and/or in a vacuum and the material heated or baked for a time and at a temperature suflicient to cure it, that is, to bring about chemical reaction between the compound and the textile. If desired, curing may be carried out simultaneously with solvent removal or drying. The cured material may be washed to remove unreacted material and undesirable by-products of the reaction.

The conditions for carrying out the impregnation depend upon the nature of the material being treated, the compound and the concentration of the treating solution, and the type of finish desired. Thecompounds are ordinarily employed in the form of an aqueous solution or dispersion. However, if tightly woven fabrics are to be treated, it is frequently advantageous to add to the treating solution a small quantity of alcohol, acetone or a wetting agent of the cationic or nonionic type. Solutions of the compounds in organic liquids, such as benzene, ethyl alcohol, and ethylene dichloride, may also be employed.

The concentration of the treating solution depends upon the material being treated and the result desired. Soft finishes which impart only a'small degree of water repellency are obtained When when the" treating: solution. contains betweerm about 0.1 percent and about 0.5. percent ofthe; compound while highly water repellent: soft-.fin-

ishes are obtained when the concentration is'between about 0.5 percentand about-20 percent compound depending upon the structure of the compound employed. The material may -also-be= rendered dimensionallystableby use of treating solutions of these'concentrations. These figures;- are based on a percentv pickup of treating:v solution by weight'of the fabric being treated.

If a lower pickup is obtained, the concentration-r of the treating solution should be increased'proportionately. This is particularly true; foriex ample, when tightly woven; fabrics are; being; treated.

In order to prevent or minimize loss intensile strength and tendering when cellulosic materials are treated with the compounds of the invention, the pH of the treating solution should-bead justed so that the cured treated material has a pH between 5 and 8.0, preferably 6 and 7. The:- pH of the cured materialis considered as equiva-- lent to that of the Water extract obtained-by= immersing 20 grams of the cured material in'500 cc. of water for one-half hour. In most casesit will be found that the cured material has a pH the same as or slightly more acid thanthe' treating solution since the acid by-products' of the chemical reaction between the material and the compound are usually volatile and are largely lost during curing. The pH of the treating solu-- tion therefore should be in the rangeof "5 to-lO. Buifers, which preferably are non-volatile at thecuring temperature used, and inert-both to-the compounds of the invention and to the textilematerial, are employed to maintain the pH'ofthe treating solution at the desired value; De pending upon the pH of the'initial treating solution, bases such as triethanolamine, diethanolamine, sodium acetate, ammonium acetate, pyri'-' dine, hexamethylene tetramine, and sodium formate, or acids such as lactic, glycolic or alpha. hydroxybutanoic acids may be used to adjust the-- pH of the initial solution.

Other textile finishing agents maybe added to" the treating solution to give a fuller orstiiler handle to the material. Substances such as-ammonium acetate, carragheen moss, gum tragaeanth, natural resins and waxes, ammonium stearate or water-soluble cellulose derivatives, such as methyl, hydroxyethyl and sodium car.-- boxymethyl cellulose, may be added. Additional waterrepellent compounds may be added if 'desired. Preferably cationic quaternary ammonium compounds which are closely related to the compounds of the invention are employed, for example, octadecyloxymethylpyridinium chloride, N,N -di (chloropyridiniummethyl) paraphenylene di-carbamate, stearamidomethylpyridinium chloride andhexamethylene or decamethylene di(oxy-- methylpyridinium chloride). W'here these-addi tional agents are insoluble in water, they are frequently dispersed in the treating-solution'by the quaternary ammonium compounds of -the-invention, which also have detergent'properties.

The treating operation is preferably carried out at temperatures below 40 C. where the com-- pounds of the invention are readily decomposed in aqueous or organic solvent solutions or dispersions. More stable compounds may be applied at more elevated temperatures, in some cases even at the boiling point, but even the most stable compounds tend to become acid when kept at such temperatures forany extended period oftime;

7. and give a less satisfactory finish, not as resistant to organic solvents. In general, therefore, the treating operation is carried out at between and C.

The treatment is carried out by padding or soaking the material in the treating solution or dispersion. Conventional 2 or 3 roll padders may be used. The material is preferably subjected to pressure during or after treatment in order to insure thorough impregnation. Surplus liquor is removed by squeezing or hydroextracting. When the textile material is being dimensionally stabilized and/or crease-proofed, an effect obtained with certain of the compounds of the invention, particularly the urea derivatives, it is then stretched while still wet to the desired finished dimensions and then drying and baking are carried out while the material is under tension. This stretching step is unnecessary when the material is merely to be rendered water-repellent.

In this connection, it should be noted that the effects of the treatment are not always entirely fast to severe laundering. For this reason it is important that the treatment be applied to the fabric in it normal, relaxed state. After treatment and curing are carried out with an overstretched fabric, then the latter will be stabilized at its extended size. When the stabilization effect is worn off on laundering the fabric will then shrink to its normal relaxed size. On the other hand, if the process is carried out on a fabric in its relaxed state, the gradual loss of finish during laundering will not cause shrinka e.

Many of the compounds of the invention are readily hydrolyzed by water at temperatures above about 80 C. Therefore, if the impregnated textile material is heated at temperatures above 80 C. while still wet, premature decomposition of the quaternary ammonium compound may occur, and no water repellency may thereafter be obtained. This is particularly true of thick or tightly woven fabrics which tend to retain moisture for a long period of time, even at elevated temperatures, thus facilitating the hydrolysis of the quaternary ammonium compound. In such cases, it is best to first dry the fabric thoroughly so that baking and curing may be carried out in the absence of moisture. The drying temperature is preferably between 30 and 80 C., but the temperature of drying is less important than the speed and other conditions. If the fabric is dried in more or less stagnant air as in an oven, without artificial circulation, it should not be submitted to a drying temperature of more than 30 C. When, on the other hand, it is dried in a blast of hot air so that the water may be removed rapidly, say in about 3 minutes, then the drying temperature may rise to 80 C. Again, when the treated material is dried on a steamheated cylinder at 120 C., no permanent water repellency may be obtained.

The baking or curing treatment is essential to the development of permanent softness, water repellency, dimensional stabilization, and creaseresistance. The term permanent refers to the resistance of the finish to laundering and dry cleaning operations. A good finish may be obtained if the baking step is omitted, but it wil1 not be permanent.

The curing or baking temperature should be between 80 and 200 0., preferably between 100 and 150 C. The time of baking is inversely proportional to the temperature used, and both depend to some extent on the nature of the comagent is applied alone.

formed in situ by impregnation of the textile ma-- 8 pound and of the textile material. A longer baking time and a relatively low temperature should be used with thick or tightly woven fabrics in or der that the heating may be uniform throughout, while open weave fabrics may safely be heated for a very short time at a higher temperature. If tenderin of the material is to be avoided, the time of baking is preferably kept as short as possible and the baking temperature as low as possible.

In the case of open weave fabrics, if a brisk circulation of air is provided around and through the material, the preliminary drying step may be;

omitted and the treated material heated at once at the baking or curing temperature.

The drying operation may be carried out in a covered tenter frame, while curing or bakingis best carried out on a loom, mat, roll or air lay dryer.

After baking or curing, the material is givena light soap wash, preferably with the addition ofa Small proportion of base, such as ammonia, to remove undecomposed quaternary ammonium salt, together with any of its water-soluble decomposition or reaction products and bufier compounds. Frequently, no water-repellency or dimensional stability is apparent until this is done.

The new quaternary ammonium compounds may also be used in conjunction with synthetic resins to make the textile material being treated crease-resistant. In conjunction with such ma-' terials, the compounds impart softness and suppleness, thus preventing the harshness and stiffness which results when the crease-resistant A synthetic resin is added to the resin solution, or the textile treated therewith, before or after treatment with the resin.

Example 1 Pyridinium hydrochloride is prepared by dissolving pyridine in benzene, passing in dry, gaseous hydrogen chloride and filtering off and drying the precipitated salt.

A mixture containing one mole of the cyclopropyl carbinol ether of dimethylol urea, 100 parts of percent ethyl alcohol and 1.2 moles of pyridinium hydrochloride is reacted at 70 C. for 30 minutes, giving a clear solution. The solution is evaporated at 40-50 C. to leave as a residue a water soluble product which is identified as the pyridinium salt of cyclopropyl methyl ether' of dimethylol urea,

CH2 l oncrno cmNno ONHOH2NC5H5C1 C Upon heating a sample of the dried powder at C. fumes of pyridine are given off and an amorphous, water insoluble solid is obtained. Anaqueous solutionv is even more rapidly and easily,

9'- dissociated when heated above90 C. and deposits atwater, insoluble film on the bottom of a shallow dislrcontaining'the solution. Upon baking the dish at 135 C., this film is further converted to an iniusible resin.

Ten parts by weight of the dried powder are dissolved in 30 parts of hot 95 percent ethyl alcohol and diluted with 100 parts of warm water. 80 x 80 cotton cloth and spun rayon challis cloth are padded .in the solution, passed between rollers set to retain a weight of solution equal to the weight of the cloth, dried and cured by heating irran ovenfor 7 minutes at 135 C., washed minutes in a one percent soap solution, dried and ironed. Both samples of treated cloth are then very soft and have excellent permanent water repellency, together with some crease resistance and shrinkage resistance.

Example 2 Dry hydrogen chloridegas is introduced into a mixture heated to 40 C. and containing one mole of cyclopropionamide, 150 g. of benzene and onemole of paraformaldehyde, until formation of the chloromethyl compound, which can be clearly recognized by the benzole solution becoming clear. The water from the reaction which accumulates at the-bottom of the vessel is run ofi. The benzene and surplus hydrochloric acid are driven oif in a vacuum and the chloromethyl compound obtained is stirred with 1.5 moles of pyridine. The precipitate which forms is separated and dried in vacuo.

The cyclopropionamido methylene pyridinium chloride'is dissolved in-water to give a 6 percent solution, whose pH is adjusted to 8.0 by addition of "sodium phosphate-solution. A 5050 rayoncotton-cloth padded with this solution'to'give a- 100 percent pick-upby weight, dried at 70 C. for-=15 minutes and then baked at about 130 C. for 5 minutes. The resulting product shows good and permanent water repellency.

Example 3 One mole of w-cyclopropyl decamethylene cyanide is dissolved in 100 g. of benzene and one mole of paraformaldehyde added. The nitrile may be prepared from the corresponding acid by forming the amide and then reacting the latter with P205. Dry hydrogen chloride gas is introduced at ordinary room temperature until the chloromethyl imino ether is formed. The benzene and surplus hydrochloric acid are removed by suction in a vacuum at a temperature of about 40-50 C. and the chloromethyl compound then stirred with two moles of pyridine. The water soluble'quaternary pyridinium salt of the chloromethyl imino ether is produced, of the formula Example 4 To 250 parts of pyridine, 23 parts of dry hydrogen chloride gas are added. One mole of cyclopropylcarbamyl hexamethylene isocyanate (prepared by reacting oyclopropyl carbinol and hexamethylene diisocyanate) and one mole of paraformaldehyde are added and the mixture is stirred and heated at C. until a test sample of the reaction mixture gives a clear solution in water. The reaction mixture is cooled and ether is added, whereby the new compound is precipitated in colorless crystals. The compound has the for mula,

01101120 0 CNH(CH2)0NHC O O CHzNCsHsCl A suiflcient quantity of the compound is dissolved in water to give a 10 percent solution. A rayon fabric is padded with this solution at room temperature to a percent pick-up by weight, dried at 75 C. for 30 minutes and then baked at C. for 30 minutes. The resulting fabric shows a high degree of permanent water repellency, and some dimensional stability.

Example 5 To parts of dry pyridine 40 parts of dry gaseous hydrogen chloride are added. One mole of paraformaldehyde and one mole of cyclopropionyl urea (prepared from urea and cyclopropicnic acid) are then added and the mixture is stirred and heated at 7075 C. until after about 18 hours a test sample gives a clear solution in warm water. The mixture is then cooled and acetone is added, whereby the new compound is precipitated as colorless crystals. It is readily soluble in water at 60-70 C. to give a clear, foaming solution. When this solution is kept hot, decomposition takes place, a precipitate is formed and the tendency to produce'foaming is lost. The compound has the formula:

CH0 ONHC ONHCHINCsHsCl This compound is dissolved in water to give a-3 percent solution and a cotton cloth padded therewith to a 100 percent pick-up by weight. The cloth isthen dried at 60- C. for one-half hour and baked at 90 C. for 5 minutes and then at not over C. for 20 minutes. The resulting product shows a high degree of permanent water repellency, dimensional stability and crease-resistance.

Example 6 3.6 moles of hydroxy butyl urea (prepared from 1,4-butanediol and urea) is placed in a threeneck flask fitted with an addition funnel, stirrer and hydrochloric acid gas exit tube and cooled to 0 C. 2.3 moles of allyl bromide and chlorine are added simultaneously at such a rate that the mixture remains just on the green side while the temperature is held at about 0 C. Upon completion of the reaction, air is introduced to expel the hydrochloric acid; thereafter the balance of the acid is removed under vacuum with application of heat. The reaction mixture is then distilled under vacuum to recover the l-chloro, 3-bromo, 2-butoxyurea propane.

To effect cyclization, about 19.5 grams of zinc dust are added with vigorous stirring to about 70 grams of water placed in a three-neck flask fitted with a funnel, stirrer and condenser, and the flask is heated to reflux temperature. 0.7 mole of the ether is added drop by drop and refluxing continued at a moderate rate. The product is extracted from the water layer with ethyl ether 11 and dried over sodium sulfate. The ether is then removed and the product recovered.

To 130 parts of dry pyridine dry hydrogen chloride is added. One half mole of paraformaldehyde and 0.5 mole of N-cyclopropyloxytetra methylene urea CH1 )CHO GHICH2CHZCHIONHC ONH: CH2

are then added and the mixture is stirred and heated at 60-65 C. until a test portion gives a clear, foaming solution in warm water. The reaction mixture is then cooled and ether is added, whereby the new compound is precipitated in colorless, very hygroscopic crystals. This has the formula:

I CHOCH1CH2CH2CH3NHCONHCHzNCsHsCi Suflicient compound is dissolved in water to produce a 4 percent solution, which is then padded on a 100 percent rayon fabric and on a 50 percent rayon-50 percent wool fabric to a 100 percent pickup by weight. Both cloths are then dried at 70-80 C. and baked at from 120 to 140 C. for 15 minutes. The resulting products are permanently water repellent and show good dimensional stability.

Example 7 200 parts of ethylene chlorohydrin and 220 parts of dry Pyridine are heated together for 24 hours at 100 0., care being taken to exclude moisture. Into the hydroxyethyl pyridinium chloride thus produced one mole of /CH(CH2)11COCI CH2 (cyclopropylauryl chloride) is allowed to run gradually while stirring, the reaction mixture being maintained continuously at water bath temperature. The reaction is continued until a sample is soluble in water to a clear solution. The product thus obtained is believed to have the formula:

/CH(CH2)1|C O CHzCHrNCsHsC] OH:

The product is dissolved in water in sufficient quantity to give a 6 percent solution and the pH adjusted to 8.0 with triethanolamine. A viscose rayon fabric is padded with this solution to a 100 percent pick-up by weight, dried at 60 C. and baked at not over 140 C. for minutes. The product shows a water repellency and shrinkage resistance which are permanent to washing with soap and alkali.

Example 8 12 and yields a crystalline, readily filter-able product which may be recrystallized from alcohol, and which is readily soluble in dilute alkali and in hot water. This product is cyclo propylstearamidomethyl phosphonic acid,

Cotton fabric is treated with an aqueous 4 percent solution of the ammonium salt of the above phosphonic acid and then heated at not over 150 C. for a few minutes. The fabric acquires a soft feel and is strongly water repellent. These properties are not lost when the fabric is washed. The fabric is also crease-resistant.

Example 9 One mole of cyclopropionyl urea (which may be prepared by condensing cyclopropionic acid with urea) is suspended in 125 parts of ethylene dichloride with one mole paraformaldehyde, one mole of dimethyl ethyl amine hydrochloride and 0.4 part triethyl amine. The mixture is warmed for five hours at 60 C., with stirring. Upon removal of the solvents a water soluble product is obtained which dissolves in warm water to form a somewhat cloudy solution having foaming properties. This product is believed to have the formula:

When the aqueous solution of' this product is made alkaline, a precipitate is quickly formed which is insoluble in methanol or acidified water.

Cotton or wool material is impregnated with an aqueous solution of this product, dried at about 60 to C. and then heated to a temperature between and C. in an oven with rapid circulation. The material acquires a water repellent finish which is permanent in the sense that it is not removed by laundering with soap and alkali.

Example 10 A mixture of pyridine hydrochloride and pyridine is made by passing gaseous hydrogen chloride into 100 parts of pyridine until an increase in weight of 9.1 parts is obtained. To this mixture are added one mole of paraformaldehyde and one mole of on, on, \CHCHO HC{ I Cz \CH:

The mixture is stirred and heated at 60 C. for 4 hours. The reaction mass is then cooled and mixed with an equivalent amount of ethyl ether, and the lower oily layer which separates is removed and washed with a further quantity of ether. The washed oil is then shaken up with cold chloroform, allowed to stand and the lower layer separated off and washed with ether. The quaternary pyridinium salt is obtained, corresponding to the formula:

CHO CHaNCnHI .I'I'his-compound is dissolved in water to give The resulting Example 11 One mole of cyclopropyl octamethylene alcohol and one-mole of paraformaldehyde are suspended vin 120 parts of dry benzene. ..''chloride is passed into the stirred mixture, keep- ;ing' the temperature below C. until a clear Gaseous hydrogen benzene solution is obtained. The lower aqueous layer is then removed and the upper benzene layer dried with calcium chloride. The benzene is re- :moved and the residue recovered. The new compound is believed to have the formula:

CH(CH2);OCH;GI

.This product is dissolved in dry pyridine. The -solid pyridinium chloride is readily soluble in wa- .ter and alcohol.

.Suflicient compound is dissolved in water to :givea 3 percent solution, which is then applied to 100 percent wool andcotton fabrics at room temperature. The fabrics are dried at 50 C. and then baked at not over 150 C. for minutes.

.The products are permanently water repellent and dimensionally stable.

Example 12 One mole of cyclopropionamide is heated with 0.6 mole of chloromethyl ethyl ether for 3 hours at 90 C. with stirring, at which time evolution of hydrogen chloride is complete. Excess chloromethyl ether is removed by distillation. The residue is dissolved with one mole of paraformaldehyde in benzene and heated until when a test portion is cooled, no solid is seen to separate. The mixture is allowed to settle and the benzene solution is removed from the lower aqueous layer. The benzene is then distilled off under reduced pressure and the dichloromethyl compound recovered. This is dissolved in 200 parts of ethyl acetate and the solution mixed with an excess of pyridine. A white precipitate is obtained which is filtered off and dried. The white powder thus recovered dissolves in hot water, forming a clear, foaming; solution, and is soluble in alcohol and in hot benzene and acetone. The compound appears to have the formula:

lency and dimensional stability, and are crease resistant.

Example 13 A solution is made by dissolving 100 parts of urea in 200 parts of neutralised aqueous formaldehyde solution (40 percent), to whiohrisadded 7.5 parts of concentrated ammonia solution (Sp. Gr. 0.880). The mixture is boiled for a few minutes and then rapidly cooled to room temperature. There are now added 6 parts of ammonium dihydrogen phosphate and 8 parts of cyclopropionyl ureido methylene pyridinium chloride in the form of an aqueous suspension in 50 parts of cold water and the mixture is diluted to a-total volume of 400 parts by addition of cold water.

Cotton sheeting is padded in the above solution at room temperature and is then squeezed so that it contains its own weight of impregnating solution. It is then dried in a current of warm air at 40-50 C. The dry fabric is heated for a few minutes at not over 150 C. Finally it is washed for a few minutes at 45 C. in a solution containing 2 parts of soap and 1 part of anydrous sodium carbonate in 1000 parts of water, well rinsed in warm water and dried.

The fabric now has a remarkably soft handle,

is highly water repellent and is crease-resistant.

These properties survive washing and dry cleaning treatments.

Example 14 Ten parts by weight of cyclopropyl carboxyethylene oxymethylene pyridinium chloride CHCOGH2CH2oCH2NC5H5C1 Ce.

(prepared from cyclopropyl methyl ketone, paraformaldehyd and pyridine in the presence of dry HCl) are dissolved in 30 parts of hot percent ethyl alcohol and diluted with parts of warm water. 80 x 80 cotton cloth and spun rayon challis cloth are padded in the solution passed between rollers set to retain a weight of solution equal to the weight of the cloth, dried at 80 C. and cured by heating in an oven for about 15 minutes at not over C., washed 15 minutes in a one percent soap solution and then dried. Both samples of treated cloth are then very soft and have excellent water repellency and dimensional stability.

The following is claimed:

1. Compounds having the general formula:

)P '(R)n OHIN(t1't)X 0%:

where R is a bivalent radical selected from the group consisting of an: o, -oo -ooo CONH,CO,NHCOO,

NHO ONH, co: nc ONH-, OCHzNHCONH- and --CH2OOCNH.-, A is a hydrocarbon radical containing from 1 to 20 carbon atoms, N(tert) is pyridine, X is an anion and m, n, and p are numbers selected from the numbers 0 and 1, provided that m, n and 22 cannot all be 0 and that when m and n are both 1, p is also 1.

2. Quaternar ammonium compounds having the formula CH(CHZ)CONHCHZNC5H5X wherein n is an integer from 1 to 20, and X is an anion.

3. Quaternary ammonium compounds having the formula:

CH(CH:),.NHC ONHCHzNCsHS wherein n is an integer from 1 to and X is an anion.

CH0OCNH(CH1),.NHCOOCH1NC5H5X wherein n is an integer from 1 to 20 and X is an anion.

5. A process for treating organic textile materials to enhance the Water repellency, creaseproofness and dimensional stability thereof which and -CH2OOCNH-, A is a hydrocarbon radical containing from 1 to 20 carbon atoms, N(tert) is the residue of a tertiary amine, X is an anion and m, n, and p are numbers selected from the numbers 0 and 1, provided that m, n and 11 cannot all be 0 and that when m and n are both 1, p is also 1, said solution being applied in suflicient amounts to cause from 0.05 to 20 per cent of said compound to be deposited on said material based on the weight of the material when dry, said solution having a pH of from 5 to 10 and a temperature of below C., drying said impregnated material at a temperature of from 30 to C. and heating the material to a temperature from 80 to 200 C.

6. The process as in claim 5 wherein said organic textile material is cellulosic.

7. The textile material made by the process of claim 5.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,125,901 Evans et al. Aug. 9, 1938 2,131,362 Baldwin Sept. 27, 1938 2,146,392 Baldwin Feb. 7, 1939 2,189,664 Katz-man Feb. 6, 1940 2,209,383 Bock July 30, 1940 2,291,021 Bock Jul 28, 1942 FOREIGN PATENTS 7 Number Country Date 547.8 16 Great Britain Sept. 15, 1942 

1. COMPOUNDS HAVING THE GENERAL FORMULA: 